JPS591217A - Manufacture of metal-clad fiber reinforced plastic sheet - Google Patents

Abstract

PURPOSE:To obtain a metal-clad FRP sheet excellent in chemical resistance, heat resistance, toughness by impregnating reinforcing fiber base with resinous liquid of electron ray hardening compound containing an ethylene unsaturated bonding, sticking a metal foil on one side of the reinforcing fiber base and irradiating electron rays from the side opposite to the metal foil-clad side. CONSTITUTION:Reinforcing fiber base is impregnated with resinous liquid of electron ray hardening compound containing an ethylene unsaturated bonding, metal foils are stuck on one side of the reinforcing fiber base impregnated with resinous liquid and then electron rays are made to irradiate from the side opposite to the metal foil-clad side. In this manner, a metal clad FRP sheet excellent in chemical resistance, heat resistance, mechanical characteristics can be menufactured with excellent productively.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an improved metal-clad fiber-reinforced plastic sheet (hereinafter referred to as "metal-clad VXPV-H").Method for producing a metal-clad FRP sheet that is solvent-free and highly productive I: It is related to

The conventional manufacturing method for metal-clad IFRP sheets is to first make an FRP sheet, and then 4: apply a bonding agent to metal foil or FR.
After coating on P-rate and heat drying 4: Remove the solvent, it is laminated with copper foil.

In addition, the manufacturing method for the conventional metal-clad vRPv-) (two-sided FRP sheet is Evoki V resin). 4: This is a method of impregnating, then heating to perform preliminary curing, removing the volatile solvent, and then heating and pressing using a press to mold.This method is a complicated process, and
Productivity is poor.

On the other hand, unsaturated polyester resins are the most commonly used FRP resins, both quantitatively and in terms of the wide range of fields in which they are used. Unsaturated polyester resins can be cured at room temperature and do not produce by-products during curing, so they do not necessarily require pressurization and have the advantage of being able to be molded in a variety of ways.
It is inferior in physical properties such as chemical resistance, heat resistance, electrical properties, and toughness.

In order to solve the drawbacks of such conventional methods, the present inventors conducted research and found that they cured a reinforcing fibrous base material impregnated with a resin liquid of an electron beam curable compound containing an ethylenically unsaturated bond and bonded a metal foil. The present invention was completed by discovering that the chemical resistance, heat resistance, and mechanical properties of a metal-clad FRP sheet obtained by irradiating layers with electron beams are significantly superior to those of conventional sheets. It is.

That is, in the present invention, a reinforcing fibrous base material is impregnated with a resin liquid of an electron beam curable compound containing an ethylenically unsaturated bond, and then one side 4 of the reinforcing fibrous base material impregnated with the resin liquid is metal. After pasting the foil together, start from the side opposite to the side where the metal foil was pasted! The gist of this invention is a method for manufacturing metal-clad fiber-reinforced plastic sheets, which is characterized by irradiation with sub-beams.

The present invention will be explained in detail below.

Examples of the electron beam curable compound containing an ethylenically unsaturated bond used in the present invention include prepolymers or oligomers having an ethylenically unsaturated bond in the molecule, such as unsaturated polyesters, polyester acrylates, epoxy acrylates, urethane acrylates, polyesters, etc. Monomers with ethylenically unsaturated bonds in the molecule, such as various acrylates such as ether acrylate, polyol acrylate, and melamine acrylate, various methacrylates such as polyester methacrylate, epoxy methacrylate, urethane methacrylate, polyether methacrylate, polyol methacrylate, and melamine methacrylate. , for example, styrenic mono-r-s such as ethylene and a-methylstyrene: methyl acrylate, 2-ethylhexyl acrylate, methoxyV-ethyl acrylate, butylV-ethyl acrylate, butyl acrylate, acrylic acid Acrylic esters such as methoxybutyl and phenyl acrylate; Methacrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxytityl methacrylate, phenyl methacrylate, and lauryl methacrylate; acrylamide; Unsaturated carboxylic acid amides such as methacrylamide; 2-(N,M-dimethylamino)ethyl acrylate, 2-(N, methacrylate);

N-dimethylamino)ethyl, acrylic acid 2-(NUN
-dibenzylamino)ethyl, methacrylic acid (N*N
-dimethylamino)methyl, acrylic acid 2-(MeN-
Substituted amino alcohol esters of unsaturated acids such as diethylacet)) propyl; ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate), 114-hexane diol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate One type or a mixture of two or more types of polyfunctional compounds such as acrylate, dipropylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, and diethylene glycol dimethacrylate can be used.

If a compound with a low cohesive force is used as the above electron beam curable compound, a relatively hard and brittle IFRPV-toshi cannot be obtained.In this sense, a compound with a high cohesive force is desirable. It is preferable to have a high molecular weight and a polar group, such as bisphenol type epoxy acrylate and novolak type epoxy acrylate as shown in the following formula.

(IaL7'll # I 1 (7-We: ) The main chain of epoxy acrylate is epoxy resin, so the FRP sheet obtained has excellent corrosion resistance.High molecular weight epoxy acrylate is solid or viscous. Although it is often a highly concentrated liquid, it has the advantage that there is a wide range of vinyl hexamers to choose from for dilution.

Further 6: By changing the main chain of the epoxy acrylate cured product, various cured products can be obtained from those with high rigidity to those with high flexibility, and can be adapted to various uses.

Alternatively, 5 in the molecule: Ethylenically unsaturated bond I is subjected to treatment such as trimethylsilylation, urethanization, and helogenation before use 1: Can it be obtained? The water resistance of the RP sheet can be improved.

A thermoplastic resin may be added as an optional component to the above-mentioned electron beam curable compound containing an ethylenically unsaturated bond (as long as it does not hinder its curing. Such thermoplastic resins include ethyl cellulose, Ethyl hydroxyethyl cellulose, cellulose acetate propionate,
Cellulose derivatives such as cellulose acetate, polystyrene,
Styrene resins and styrene copolymer resins such as poly-methylstyrene, acrylic or methacrylic resins alone or copolymer resins such as polymethyl methacrylate, polyethyl methacrylate, polybutyl acrylate, rosin, rosin-modified maleic acid resin, Rosin-modified phenolic resins, rosin ester resins such as polymerized rosin, polyvinyl acetate resins, coumaron resins, vinyl toluene resins, vinyl chloride resins, polyester resins, polyurethane resins, butyral resins, and mixtures of several of these resins. can be used.

An electron beam curable compound containing the above-mentioned ethylenically unsaturated bond, a thermoplastic resin added as an optional component as necessary,
Other suitable ingredients such as a surfactant, a plasticizer, and a coloring agent are added and kneaded using a propeller stirrer, a kneader, a sand mill, a three-roll mill, or the like to obtain a resin liquid.

Next, the reinforcing fibrous base material ζ is impregnated with the above resin liquid.

Examples of the reinforcing fibrous base material include paper, non-woven fabrics and woven fabrics made of organic fibers such as polyester, acrylic, and polyamide, and inorganic fibers such as glass fibers, carbon fibers, and hollow boron fibers. can be used. For impregnation, use the above resin liquid,
Known method C: This is carried out for the above-mentioned reinforcing fibrous base material C. One example of the method is to use an impregnating device equipped with an impregnating head and a sifting roller or doctor for controlling the amount of impregnation. In addition, roll coaters, hot melt coaters, etc. can also be used.

Assuming that the coated material containing the base material is 1001%, the coating amount can be 101% to 90%, and preferably 4091% to 60%, depending on the porosity of the base material and the necessary physical properties i2.

As described above, C: After impregnation, metal foil is pasted on one side of the reinforcing fibrous base material impregnated with resin liquid, and then an electron beam is irradiated from the side opposite to the side where the metal foil was pasted. do.

As the metal, single metals such as iron, copper, lead, aluminum, zinc, tin, gold, silver, platinum, etc., and composite metal foils such as plated steel sheets such as galvanized iron and tinplate can be used. The lamination is performed by a known method, and the electron beams used include various types of electron beam acceleration such as Cockroft-Walton type, bumpgraph type, resonant transformer type, insulated core transformer type, linear type, dynamidron type, and high frequency type. Released from the aircraft, 50 to 100
An electron beam with an energy in the range of 0 KeV, preferably 100 to 300 KaV is used, and the irradiation dose is 1
~20 Mra4 is preferable; below I Mrad, curing is insufficient and viscosity remains, while above 60 Mra, decomposition reaction due to electron beam irradiation progresses, resulting in deterioration of physical properties such as chemical resistance and mechanical properties. While a reinforcing fibrous base material impregnated with resin liquid and laminated with metal foil is continuously run, a continuous curtain-shaped electron beam is normally irradiated from a linear filament to the side without metal foil. , it becomes possible to continuously cure the reinforcing fibrous base material impregnated with the resin liquid and to integrate it with the metal foil.

The method of the present invention basically consists of the above steps, but the following steps may also be added.

First, a resin liquid of an electron beam curable compound containing an ethylenically unsaturated bond is applied to the surface of the metal foil in advance, and then the applied surface of the metal foil and a reinforcing fibrous substrate impregnated with the resin liquid are applied. This is the process of pasting the materials together. In this way, the contact force between the metal foil and the reinforcing fibrous base material is improved.

As the electron beam curable compound constituting the resin liquid applied to the metal foil, it is preferable to use a compound with a highly polar functional group and a high cohesive force. For the purpose of lowering the viscosity during coating and further increasing the polarity, for example, 2-hydroxyethyl acryloyl phthalate, 3-
Low viscosity electron beam curable compounds with carboxyl groups such as hydroxyprobyl acryloyl succinate, 2-hydroxyethyl acryloyl phthalate, diphenyl 2
- It may be diluted with a low-viscosity electron beam-curable phosphorus compound such as acryloyloxyethyl phosphate, bis(2-chloroethyl)vinylphosphonate, and ethyl acryloyl phosphate. However, even if these diluents are added in amounts of 20 or more, they do not contribute to improving the contact force.

The amount of the electron beam curable compound applied to the metal foil in advance is C: 10? in order to improve the contact force. /- or more resin liquid C required and impregnated into the reinforcing base material: large amount d:
In order to prevent mixing, it is desirable that it be 50 P/It'' or less.

Secondly, prior to electron beam irradiation, a releasable film is closely placed on the side opposite to the side to which the metal foil is pasted.

Due to the viscosity of the surface of the reinforcing fibrous base material impregnated with a resin liquid, it easily attracts dust, and the resin liquid contaminates the roll method of manufacturing equipment. In order to eliminate such obstacles, after laminating the metal foil to the reinforcing fibrous base material impregnated with resin liquid, or at the same time as laminating it, a releasable film is applied using a laminator or the like on the side opposite to the side to which the metal foil is laminated. book! Examples of removable films include polyvinylidene chloride, polyvinyl chloride, ethylene/vinyl acetate copolymer, polytetrafluoroethylene, polystyrene, polyethylene, polypropylene, polymethyl methacrylate, polyethylene terephthalate, polycarbonate, polyamide, etc. A general film can be used, and one having a thickness of 12 to 100 μm is preferable.

One side C of a reinforcing fibrous base material made by impregnating the above film with a resin liquid: The effect of electron beam irradiation does not substantially decrease even if it is kept under close observation, but rather it is exposed to air under close observation with the film. Therefore, the curing is not inhibited by oxygen C in the air during electron beam irradiation, and preliminary curing is effectively performed.

Since the present invention has the above-mentioned configuration, the electron beam curable compound is completely cured in a very short time by electron beam irradiation.
The heat drying and hot press steps required in the manufacturing process are not necessary, and the time required for manufacturing can be shortened.

In addition, due to the reaction with electron beams, crosslinking of side chains in addition to unsaturated bonds of molecules progresses, resulting in improved chemical resistance, heat resistance, and toughness.

Further C: The electrical contact between metal foil and reinforcing fibrous base material is also electronic iIj.
Since curing by &= is performed simultaneously with I=, the time required for the work is shorter and productivity is higher than in the conventional method of laminating metal foil and FRP sheet with an electrically conductive agent.

EXAMPLES The present invention will be explained in more detail below with reference to Examples.

Example 1 2#2F-bis(2-methyl-5-hydroxy-6-acroxydibrobioxyphenyl)propane at 40°C
: Glass woven fabric (manufactured by Nitto Boseki, WII) is melted while heating.
t18K)l: Impregnation rate 40% C: After impregnation, copper foil (manufactured by Fukuda Metal Foil and Powder Industries, 〒7, thickness 35μ) was laminated with an electron beam irradiation device (manufactured by WaX,
Electro curtain OB 200/50/S
Q), acceleration voltage 175Kv, irradiation dose 20M
A metal-clad IFRP sheet was obtained by irradiating an electron beam from the side opposite to the side to which the copper foil was laminated under conditions of raa.

Example 2 190 parts by weight of bisphenol-type epoxy resin (manufactured by Shell Chemical Co., Ltd., Ebicor) 828, epoxy equivalent of about 190), 72 parts by weight of acrylic acid, and 5 parts by weight of pyridine were added to BOo.
The mixture was heated at C for 3 hours to react.

The obtained reaction product was heated to 70°C, and copper foil (T-7 manufactured by Fukuda Metal Foil and Powder Industries, thickness 35μ) (: 50P/vIs
It was applied at the rate of

C2292#-bis(2-methyl-5-hydroxy-
6-Acryoxydiprobioki V-phenyl)propane 4
Melt it while heating to 0°C and make glass woven fabric (manufactured by Nitto Boseki,
After impregnating the copper foil (wm18K) to an impregnation rate of 40, the copper foil was laminated with a laminator and exposed to an electron beam irradiation device (
Manufactured by B81, Electro Curtain OB 20015 mouth 1
50) Use L% acceleration voltage 175KV irradiation dose 20M
A metal-clad FRP sheet was obtained by irradiating an electron beam under rad conditions from the side opposite to the side to which the copper foil was laminated.

Example 3 A metal-clad FR with a smooth surface was prepared in the same manner as in Example 1, except that a polyester film with a thickness of 38μ was laminated on the side opposite to the side on which the metal foil was laminated and then irradiated with an electron beam.
A P sheet was obtained.

87-

Claims (3)

[Claims] (1) Reinforcing fibrous base material C: impregnated with resin liquid of electron beam curable compound containing ethylenically unsaturated bonds, and then metal foil is laminated on one side of the reinforcing fibrous base material C: impregnated with resin liquid. , and then irradiating an electron beam from the side opposite to the side on which the metal foil is laminated. (2) -1 side I of metal foil: A method for producing a reinforcing plastic sheet in which a resin liquid of an electron beam curable compound containing an ethylenic saturated bond is applied in advance, and the coated surface is impregnated with the resin liquid. . (3) After laminating the metal foil, or at the same time, place a releasable film on the side opposite to the side to which the metal foil was laminated, and then irradiate an electron beam through the releasable film. Special